WO2024139656A1 - 一种高离子电导率聚合物基复合固态电解质的制备及应用 - Google Patents

一种高离子电导率聚合物基复合固态电解质的制备及应用 Download PDF

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WO2024139656A1
WO2024139656A1 PCT/CN2023/128237 CN2023128237W WO2024139656A1 WO 2024139656 A1 WO2024139656 A1 WO 2024139656A1 CN 2023128237 W CN2023128237 W CN 2023128237W WO 2024139656 A1 WO2024139656 A1 WO 2024139656A1
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lithium
electrolyte
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carbonate
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尉海军
吴玲巧
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Beijing University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a solid electrolyte for lithium ion batteries, in particular to a preparation method and application of a composite solid electrolyte for building a bridge between a polymer and an inorganic material, belonging to the technical field of lithium ion battery electrolytes.
  • Lithium-ion batteries are widely used in 3C consumer electronics, electric vehicles and energy storage fields due to their many advantages such as high energy density, long cycle life and no memory effect.
  • most commercial lithium-ion batteries use conventional organic liquid electrolytes, which have huge safety problems such as volatility, flammability and explosion, which seriously hinder the wider application of lithium-ion batteries. Therefore, using solid electrolytes instead of traditional organic electrolytes is one of the effective ways to solve the above-mentioned safety problems of lithium-ion batteries.
  • solid electrolytes also have the advantages of high ionic conductivity, wide electrochemical window, wide operating temperature, and can be arbitrarily tailored or changed.
  • Patent CN 111435757 B discloses a composite polymer electrolyte, a preparation method thereof, and a lithium-ion battery.
  • the inorganic lithium-conducting material in the composite polymer electrolyte has a decreasing or increasing mass distribution along the thickness direction, which can improve the lithium ion transmission to a certain extent by improving the lithium ion concentration difference at each interface.
  • its ionic conductivity and electrochemical window still cannot match high-voltage positive electrode materials.
  • CN 110380114 B provides an organic-inorganic composite solid electrolyte, a preparation method, and an application thereof.
  • the method can improve the agglomeration problem of inorganic conductor materials, thereby improving ionic conductivity and inhibiting lithium dendrites.
  • the ionic conductivity in this patent is not high enough, and on the other hand, the ether polymer used is difficult to match the use of high-voltage positive electrode materials.
  • the purpose of the present invention is to provide a method for preparing a polycarbonate-based organic-inorganic composite solid electrolyte and its application in the field of lithium-ion batteries.
  • a functionalized coupling agent forms a chemical bond with the inorganic and organic materials, so that the inorganic solid electrolyte and the polymer are connected by the coupling agent, so that the ion conductivity and electrochemical window are improved, and the high-voltage positive electrode material is matched to show excellent cycle stability.
  • the present invention provides a high ion conductivity polymer-based composite solid electrolyte, the raw materials of which include the following components: carbonate-based polymer, inorganic ion conductor, initiator or catalyst, lithium salt and silane coupling agent;
  • the inorganic lithium ion conductor material is an inorganic solid lithium ion electrolyte, and the material contains one or a combination of at least two of hydroxyl, carboxyl or sulfur groups.
  • the selected conductive lithium salt is one or more of the following: lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium bistrifluoromethanesulfonyl imide (LiTFSI), and bis(trifluoromethanesulfonyl)methyl lithium [LiC(SO 2 CF 3 ) 3 ].
  • the initiator or catalyst is one of the following: azobisisobutyronitrile (AIBN), azobisisoheptanenitrile (ABVN), dibutyltin bis(acetylacetonate), dibutyltin dilaurate, dimethyl azobisisobutyrate (AIBME), benzoyl peroxide (BPO), platinum water (Pt).
  • AIBN azobisisobutyronitrile
  • ABSVN azobisisoheptanenitrile
  • dibutyltin dilaurate dimethyl azobisisobutyrate
  • AIBME dimethyl azobisisobutyrate
  • BPO benzoyl peroxide
  • Pt platinum water
  • step (1) (2) uniformly stirring the silanized inorganic ion conductor material, carbonate-based polymer, conductive lithium salt, and organic solvent obtained in step (1); adding an initiator or a catalyst and uniformly stirring to form an electrolyte mixture; coating or immersing the electrolyte mixture into a polytetrafluoroethylene mold containing a porous support material, and heating and curing at 60-120° C. for 4-12 hours to form a film;
  • the organic solvent selected in the above steps (1) and (2) is one or more of the following: N-methylpyrrolidone (NMP), ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylene carbonate, ethyl methyl carbonate, ⁇ -butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1,2-dimethoxyethane, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and dimethyl sulfoxide.
  • NMP N-methylpyrrolidone
  • ethylene carbonate propylene carbonate
  • butylene carbonate dimethyl carbonate
  • ethylene carbonate ethylene carbonate
  • ethyl methyl carbonate ethyl methyl carbonate
  • ⁇ -butyrolactone tetrahydrofuran
  • 2-methyltetrahydrofuran 2-methyltetrahydrofuran
  • the porous support material is one or more of cellulose non-woven fabric, polyethylene non-woven fabric, polypropylene non-woven fabric, glass fiber non-woven fabric, polytetrafluoroethylene non-woven fabric.
  • the preferred support material can improve the mechanical properties of the polymer-based composite electrolyte.
  • R2 is selected from any one of aminopropyl, aminoethyl, mercapto or urea, and the chemical bond formation process is as follows:
  • Coupling agents serve as bridges between inorganic and organic matter to provide additional ion transport channels and reduce the interface resistance between organic and inorganic substances. They utilize intermolecular interactions and stable chemical bonds to improve the electrochemical stability of polymer-based composite electrolytes. Intermolecular interactions include positive vacancy effects, dipole-dipole interactions, and hydrogen bond interactions.
  • the invention provides application of the high ion conductivity polymer-based composite solid electrolyte in lithium ion batteries.
  • the preparation of the positive electrode of a lithium-ion battery includes the following steps: grinding and mixing a positive electrode active material accounting for 50-90% by mass and a conductive agent acetylene black accounting for 5-30% by mass; adding polyvinylidene fluoride (PVDF) accounting for 1-15% by mass, 1-15% electrolyte mixed solution and 1-methyl-2-pyrrolidone (NMP) to grind and mix, and 1-methyl-2-pyrrolidone (NMP) is used to adjust the viscosity; coating on the surface of aluminum foil and drying; metallic lithium and metallic lithium alloy can be directly used as the corresponding negative electrode.
  • PVDF polyvinylidene fluoride
  • NMP 1-methyl-2-pyrrolidone
  • the polycarbonate-based polymer has high ionic conductivity, and the composite solid electrolyte has excellent ion transmission capacity and thermal stability.
  • FIG. 2 is a CV curve of the lithium-ion battery in Example 5 of preparing a high ionic conductivity polymer-based composite solid-state lithium-ion battery.
  • FIG3 is a charge and discharge curve of a solid-state lithium-ion battery assembled based on the electrolyte in Example 5 and a lithium-rich positive electrode material.
  • the above APTES@LLZTO powder 2 (4 wt%) was mixed with B2 solution and 1% of azobisisobutyronitrile (AIBN) by mass of B2 solution. After ultrasonic treatment at room temperature for 30 min, the mixture was stirred for 4 h to obtain an electrolyte mixture.
  • the evenly stirred electrolyte mixture was scraped onto both sides of the Whatman membrane; it was heated at 80°C in a vacuum drying oven for 10 hours to solidify into an organic-inorganic composite electrolyte membrane with an average thickness of ⁇ 143 ⁇ m.
  • the Whatman glass fiber membrane was used as a porous support skeleton, and the stirred electrolyte mixture was scraped onto both sides of the Whatman membrane; it was heated at 80°C in a vacuum drying oven for 10 hours to solidify into an organic-inorganic composite electrolyte membrane with an average thickness of ⁇ 142 ⁇ m.
  • the solution F2 was obtained by mixing and stirring lithium imide (LiTFSI), and the above-mentioned APTES@LLZTO powder 6 (4wt%) was mixed with the F2 solution and 1% of the mass of the F2 solution, and stirred for 4h after ultrasonic treatment at room temperature for 30min to obtain an electrolyte mixture.
  • LiTFSI lithium imide
  • APTES@LLZTO powder 6 4wt% was mixed with the F2 solution and 1% of the mass of the F2 solution, and stirred for 4h after ultrasonic treatment at room temperature for 30min to obtain an electrolyte mixture.
  • the stirred electrolyte mixture was scraped onto both sides of the Whatman membrane; it was heated at 80°C in a vacuum drying oven for 10 hours to solidify into an organic-inorganic composite electrolyte membrane with an average thickness of ⁇ 143 ⁇ m.
  • Electrolyte thickness The thickness of the block polymer electrolyte was measured using a micrometer (accuracy 0.01 mm), and the thickness was measured at 3 random points on the membrane to calculate the average value.
  • Electrochemical window A 2032 button cell was assembled by sandwiching the polymer electrolyte with stainless steel and lithium sheets, and linear voltammetry (LSV) measurements were performed with a starting voltage of 2.8 V, a maximum potential of 5.5 V, and a scan rate of 1 mV/S.
  • LSV linear voltammetry
  • Grind 240 mg of lithium cobalt oxide positive electrode and 45 mg of conductive agent acetylene black evenly for 40 minutes; add 15 mg of binder polyvinylidene fluoride, 15 mg of electrolyte mixture (Example 5) and 150 ⁇ L 1-methyl-2-pyrrolidone and grind evenly for 40 minutes; apply on the surface of aluminum foil and dry at 80°C for 8 hours under vacuum conditions; cut the electrode into discs of R 12 mm, use the organic-inorganic composite electrolyte of Example 5 as the electrolyte, and assemble a solid-state lithium-ion battery with metallic lithium as the negative electrode.

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Abstract

一种高离子电导率聚合物基复合固态电解质的制备及应用，属于锂离子电池电解质技术领域。本发明选用碳酸酯基聚合物、导电锂盐、多孔支撑材料、功能化硅烷偶联剂和无机离子导体材料复合制备有机无机复合固态电解质。聚碳酸酯基聚合物电解质具有高的离子电导率、宽的电化学窗口和高的离子迁移数；功能化的硅烷偶联剂能与聚合物及无机材料之间形成化学键和相互作用，起到聚合物和无机填料之间的桥梁作用，从而提高聚合物电解质的离子电导率和拓宽它的电化学窗口，改善固态电解质与正负极的界面接触，从而提高锂离子电池的充放电性能。适用于高电压正极材料的锂离子固态电池。

Description

一种高离子电导率聚合物基复合固态电解质的制备及应用 技术领域
本发明涉及锂离子电池固态电解质，特别是一种在聚合物和无机材料之间构筑桥梁的复合固态电解质的制备方法及应用，属于锂离子电池电解质技术领域。
背景技术
锂离子电池，因其具有能量密度高、循环寿命长、无记忆效应等诸多优点，在3C消费电子、电动汽车和储能领域得到广泛的应用。目前，商业化锂离子电池大都采用常规有机液态电解液，存在易挥发、易燃、易爆等巨大的安全问题，严重阻碍了锂离子电池的更广泛应用。因此，采用固态电解质代替传统的有机电解液是解决上述锂离子电池安全问题的有效途径之一。同时，固态电解质还具有高的离子电导率、宽的电化学窗口、宽的工作温度、可任意剪裁或变化等优点。
目前的固体电解质主要包括无机固态电解质，聚合物固态电解质，以及有机无机复合电解质。无机固态电解质具有机械强度较高、室温离子电导率高等优点；但也面临着巨大的问题，如，电解质材料的密度大，材料刚性大，界面相容性差，与电极界面阻抗大等。有机聚合物电解质因与锂金属相容性好、制备工艺简单、柔韧性好和形状尺寸可调等优点，但其离子电导率较低。所以使用单一的无机固态电解质或聚合物电解质难以满足目前锂电池的实际需求。
聚合物基有机无机复合电解质结合有机材料与无机材料优势，在离子电导率、电化学窗口、机械强度等方面都有很大的提高，解决了单一组分无法解决的问题。CN 111435757 B专利公布了一种复合聚合物电解质及其制备方法和锂离子电池，所述无机导锂材料在所述复合聚合物电解质中，沿厚度方向的质量分布呈递减或递增变化，能够通过改善各界面的锂离子浓度差，从而在一定程度上提高锂离子传输，然而其离子电导率和电化学窗口仍然无法匹配高电压正极材料。CN 110380114 B提供了一种有机无机复合固态电解质及其制备方法和应用，所述方法能够改善无机导体材料的团聚问题，从而提高离子电导率和抑制锂枝晶等。但是该专利中一方面离子电导率不够高，另一方面使用的醚类聚合物，难以匹配高电压正极材料的使用。
因此，针对现有技术存在的问题，需要提供一种新的有机无机复合固态电解质膜，制备方法简单，且保证高离子电导率的情况下，能够耐高电压的能力。
发明内容
本发明的目的在于提供一种聚碳酸酯基有机无机复合固态电解质的制备方法及在锂离子电池领域的应用。本发明提供的聚合物基复合固态电解质中，功能化偶联剂与无机和有机材料之间形成化学键，使得无机固体电解质和聚合物之间使用偶联剂进行连接，使其离子电导率和电化学窗口得到提高，与高电压正极材料匹配表现出优异的循环稳定性。
为达到此发明目的，本发明的技术方案为：
本发明提供了一种高离子电导率聚合物基复合固态电解质，原料包括如下组分：碳酸酯基聚合物、无机离子导体、引发剂或催化剂、锂盐和硅烷偶联剂；
碳酸酯基聚合物占混合物的质量分数为10-96％，功能化硅烷偶联剂占混合物的质量分数为1-50％、导电锂盐占混合物的质量分数为1-50％，无机离子导体占混合物的质量分数为1-50％，引发剂或催化剂质量分数占混合物的质量分数为1-10％。
所述碳酸酯基聚合物选自聚碳酸酯、聚碳酸乙烯酯，聚碳酸乙烯亚乙酯，聚烯丙基甲基碳酸酯，聚碳酸亚乙烯酯，聚氟代碳酸乙烯酯等聚合物中的一种或几种。碳酸酯基中C＝O双键可与硅烷偶联剂上的活泼H形成化学相互作用。
所述无机锂离子导体材料为无机固态锂离子电解质，且该材料含有羟基、羧基或硫基中一种或至少两种的组合。
所述硅烷偶联剂具有如式I所示结构：
其中R1选自甲基，乙基，丙基其中的任意一种；R2选自胺丙基，胺乙基，巯基或脲基中的任意一种。
所选导电锂盐为以下中的一种或几种：六氟磷酸锂(LiPF6)、高氯酸锂(LiClO4)、双三氟甲烷磺酰亚胺锂(LiTFSI)、双(三氟甲烷磺酰)甲基锂[LiC(SO2CF3)3]。
所述引发剂或催化剂为以下中的一种：偶氮二异丁腈(AIBN)、偶氮二异庚腈(ABVN)、双(乙酰丙酮酸)二丁基锡、二月桂酸酯二丁基锡、偶氮二异丁酸二甲酯(AIBME)、过氧化苯甲酰(BPO)、铂金水(Pt)。
所述一种高离子电导率有机无机复合固态电解质的制备方法，其特征在于，包括以下步骤：
(1)取无机离子导体材料、功能化硅烷偶联剂、有机溶剂原料搅拌混合均匀，在30-80℃下加热水解(试剂及空气中的微量水即可)，12-24小时，然后在80-120℃真空干燥箱去除溶剂，制备硅烷化的无机离子导体材料；
(2)将步骤(1)得到的硅烷化无机离子导体材料、碳酸酯基聚合物、导电锂盐、有机溶剂均匀搅拌；加入引发剂或催化剂搅拌均匀，形成电解质混合液；将上述电解质混合液涂覆到或浸入含有多孔支撑材料的聚四氟乙烯模具中，在60-120℃下加热固化4-12小时成膜；
上述步骤(1)(2)中所选有机溶剂为以下中的一种或几种：N-甲基吡咯烷酮(NMP)、碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯脂、碳酸二甲酯、碳酸乙二酯、碳酸甲乙酯、γ-丁内酯、四氢呋喃、2-甲基四氢呋喃、乙腈、1,2-二甲氧乙烷、四乙二醇二甲醚、三乙二醇二甲醚、二乙二醇二甲醚、二甲亚砜。
所述多孔支撑材料为纤维素无纺布、聚乙烯无纺布、聚丙烯无纺布、玻璃纤维无纺布、聚四氟乙烯无纺布中的一种或几种。优选的支撑材料可以改善聚合物基复合电解质的机械性能。
以带有羟基(X-OH)的无机离子导体为例，R2选自胺丙基，胺乙基，巯基或脲基中的任意一种，上述化学键形成过程如下：
偶联剂作为无机物和有机物之间的桥梁用于提供额外的离子传输通道，降低有机无机之间的界面电阻；利用分子间的相互作用及稳定的化学键提升聚合物基复合电解质的电化学稳定性，分子间的相互作用包括正空位作用，偶极-偶极相互作用，以及氢键相互作用等。
以碳酸酯基聚合物(Y-C(＝O)-O-)及R2基团为氨丙基为例，上述分子间化 学作用形成过程如下：
本发明提供了所述的高离子电导率聚合物基复合固态电解质在锂离子电池中的应用。
一种包含上述高离子电导率聚合物基复合固态电解质的固态锂离子电池，其特征在于：包括正极、负极和置于正极和负极之间兼具隔膜和电解液功能的上述复合固态电解质。
锂离子电池正极活性材料为钴酸锂(LiCoO2)、镍酸锂(LiNiO2)、锂离子氟磷酸锂、锂锰氧化物、锰酸锂、镍锰酸锂、富锂材料(LLOs)、磷酸锰铁锂、镍钴铝酸锂(NCA)、镍钴锰酸锂、磷酸铁锂(LiFeO4)、磷酸钒锂(Li3V2(PO4)3)中的一种或几种；负极活性材料为金属锂、金属锂合金、石墨、硬碳、锂金属氮化物、氧化锑、碳锗复合材料、碳硅复合材料、钛酸锂、锂钛氧化物中一种或几种。
锂离子电池正极制备包括以下步骤：将占质量分数为50-90％的正极活性材料，占质量分数为5-30％的导电剂乙炔黑研磨混合；加入占质量分数为1-15％的聚偏氟乙烯(PVDF)、1-15％电解质混合液和1-甲基-2吡咯烷酮(NMP)研磨混合，1-甲基-2吡咯烷酮(NMP)用于调节粘度；涂敷在铝箔表面，烘干；金属锂、金属锂合金可以直接作为相应的负极，其他负极制备包括以下步骤：将质量分数为45-80％的负极活性材料，质量分数为5-30％的导电剂乙炔黑研磨混合；加入质量分数为5-25％聚偏氟乙烯(PVDF)、1-甲基-2吡咯烷酮(NMP)研磨混合，1-甲基-2吡咯烷酮(NMP)用于调节粘度；涂敷在铜箔表面，烘干。
上述电解质混合液优选为上述高离子电导率有机无机复合固态电解质制备过程中形成的电解质混合液。
锂离子电池组装包括扣式电池和软包电池。
偶联剂与无机离子导体材料之间形成化学键，偶联剂与碳酸酯基聚合物之间形成分子间相互作用，降低有机无机之间的界面电阻，偶联剂作为无机物和有机 物之间的桥梁用于提供额外的离子传输通道；分子间相互作用包括形成化学键、氢键相互作用，偶极-偶极相互作用，以及正空位作用等分子间相互作用的一种或几种。无机材料与偶联剂之间形成稳定的化学键，改善了聚合物和无机导体材料之间较大界面阻抗的问题，提供了额外的离子通道，使离子电导率得到了很大的提高(室温离子电导率为3.1×10-3S cm-1)，并且具有更宽的电化学稳定窗口(5.3V/vs.Li+/Li)。
本发明的创新性和实用性在于：
1.采用聚碳酸酯基聚合物，具有较高离子电导率，复合固态电解质的具有优异的离子传输能力和热稳定性能。
2.本发明采用两步法能够有效的实现聚合物链与无机材料之间的桥梁构建，降低聚合物相和无机相之间的界面电阻，改善界面相容性，提高整体的离子电导率；另外偶联剂与无机离子导体之间形成稳定的化学键、与聚合物链的C＝O形成分子间相互作用，能够提高离子迁移数和电化学窗口，显著改善电解质与电极界面的相容性，从而提高充放电性能。
3.本发明提供的聚合物基有机无机复合固态电解质其离子电导率可高达3.1×10-3S cm-1,锂离子迁移数在0.64以上，电化学窗口高达5.3V以上。其组装的固态锂电池在高电压下表现出高达98％的库伦效率和优异的循环稳定性。
附图说明
图1为高离子电导率聚合物基复合固态电解质制备实施例1和5中的LSV图。
图2为高离子电导率聚合物基复合固态锂离子电池制备实施例5中锂离子电池的CV曲线。
图3为基于实施例5中电解质及富锂为正极材料组装固态锂离子电池的充放电曲线。
具体实施方式
以下通过具体实施例来说明本发明，提供实施例是为了更好地理解本发明，绝不是限制本发明的范围。
电解质的制备：
实施例1
将50mg表面含羟基的锂镧锆钽氧无机离子导体(LLZTO)与150mg 3-氨丙基三乙氧基硅烷(APTES)加入到2mL乙腈中搅拌得到混合溶液A1，超声30min之后，在60℃搅拌24h；然后转移到80℃的真空干燥箱去除溶剂，得到APTES@LLZTO白色粉末1；然后1g将碳酸乙烯亚乙酯、0.3g双三氟甲烷磺酰亚胺锂(LiTFSI)混合搅拌得到溶液A2，将上述APTES@LLZTO粉末1(2wt％)与A2溶液及A2溶液质量1％的偶氮二异丁腈(AIBN)混合，室温超声30min之后搅拌4h，得到电解质混合液。在聚四氟乙烯模具上，以Whatman玻璃纤维膜为多孔支撑骨架，将搅拌均匀的电解质混合液刮涂到Whatman膜的两面；真空干燥箱80℃下加热10小时固化成有机无机复合电解质膜，平均厚度为～140μm。
实施例2
将200mg表面含羟基的锂镧锆钽氧无机离子导体(LLZTO)与200mg 3-氨丙基三乙氧基硅烷(APTES)加入到4mL乙腈中搅拌得到混合溶液B1，超声30min之后，在60℃搅拌24h；然后转移到80℃的真空干燥箱去除溶剂，得到APTES@LLZTO白色粉末2；然后1g将碳酸乙烯亚乙酯、0.3g双三氟甲烷磺酰亚胺锂(LiTFSI)混合搅拌得到溶液B2，将上述APTES@LLZTO粉末2(4wt％)与B2溶液及B2溶液质量1％的偶氮二异丁腈(AIBN)混合，室温超声30min之后搅拌4h，得到电解质混合液。在聚四氟乙烯模具上，以Whatman玻璃纤维膜为多孔支撑骨架，将搅拌均匀的电解质混合液刮涂到Whatman膜的两面；真空干燥箱80℃下加热10小时固化成有机无机复合电解质膜，平均厚度为～143μm。
实施例3
将100mg表面含羟基的锂镧钽氧无机离子导体(LLTO)与100mg 3-氨丙基三乙氧基硅烷(APTES)加入到2mL乙腈中搅拌得到混合溶液C1，超声30min之后，在60℃搅拌24h；然后转移到80℃的真空干燥箱去除溶剂，得到APTES@LLTO白色粉末3；然后1g将碳酸乙烯亚乙酯、0.3g双三氟甲烷磺酰亚胺锂(LiClO4)混合搅拌得到溶液C2，将上述APTES@LLTO粉末3(2wt％)与C2溶液及C2溶液质量1％的偶氮二异丁腈(AIBN)混合，室温超声30min 之后搅拌4h，得到电解质混合液。在聚四氟乙烯模具上，以Whatman玻璃纤维膜为多孔支撑骨架，将搅拌均匀的电解质混合液刮涂到Whatman膜的两面；真空干燥箱80℃下加热10小时固化成有机无机复合电解质膜，平均厚度为～142μm。
实施例4
将100mg表面含羟基的锂镧锆钽氧无机离子导体(LLZTO)与200mg3-氨丙基三乙氧基硅烷(APTES)加入到2mL乙腈中搅拌得到混合溶液D1，超声30min之后，在60℃搅拌24h；然后转移到80℃的真空干燥箱去除溶剂，得到APTES@LLZTO白色粉末4；然后1g将碳酸乙烯亚乙酯、0.3g双三氟甲烷磺酰亚胺锂(LiTFSI)混合搅拌得到溶液D2，将上述APTES@LLZTO粉末(2wt％)与D2溶液及D2溶液质量1％的偶氮二异丁腈(AIBN)混合，室温超声30min之后搅拌4h，得到电解质混合液。在聚四氟乙烯模具上，以Whatman玻璃纤维膜为多孔支撑骨架，将搅拌均匀的电解质混合液刮涂到Whatman膜的两面；真空干燥箱80℃下加热10小时固化成有机无机复合电解质膜，平均厚度为～141μm。
实施例5
将100mg表面含羟基的锂镧锆钽氧无机离子导体(LLZTO)与100mg 3-氨丙基三乙氧基硅烷(APTES)加入到2mL乙腈中搅拌得到混合溶液E1，超声30min之后，在60℃搅拌24h；然后转移到80℃的真空干燥箱去除溶剂，得到APTES@LLZTO白色粉末5；然后1g将碳酸乙烯亚乙酯、0.3g双三氟甲烷磺酰亚胺锂(LiTFSI)混合搅拌得到溶液E2，将上述APTES@LLZTO粉末5(8wt％)与E2溶液及E2溶液质量1％的偶氮二异丁腈(AIBN)混合，室温超声30min之后搅拌4h，得到电解质混合液。在聚四氟乙烯模具上，以Whatman玻璃纤维膜为多孔支撑骨架，将搅拌均匀的电解质混合液刮涂到Whatman膜的两面；真空干燥箱80℃下加热10小时固化成有机无机复合电解质膜，平均厚度为～146μm。
实施例6
将100mg表面含羟基的锂镧锆钽氧无机离子导体(LLZTO)与50mg 3-氨丙基三乙氧基硅烷(APTES)加入到2mL乙腈中搅拌得到混合溶液F1，超声30min之后，在60℃搅拌24h；然后转移到80℃的真空干燥箱去除溶剂，得到APTES@LLZTO白色粉末6；然后1g将碳酸乙烯亚乙酯、0.3g双三氟甲烷磺 酰亚胺锂(LiTFSI)混合搅拌得到溶液F2，将上述APTES@LLZTO粉末6(4wt％)与F2溶液及F2溶液质量1％的偶氮二异丁腈(AIBN)混合，室温超声30min之后搅拌4h，得到电解质混合液。在聚四氟乙烯模具上，以Whatman玻璃纤维膜为多孔支撑骨架，将搅拌均匀的电解质混合液刮涂到Whatman膜的两面；真空干燥箱80℃下加热10小时固化成有机无机复合电解质膜，平均厚度为～143μm。
电解质厚度：采用千分尺(精度0.01毫米)测量嵌段聚合物电解质的厚度，任意取膜上3个点测量，求平均值。
离子电导率：采用两个不锈钢垫片夹住聚合物电解质，组装R2032的扣式电池测量阻抗，根据公式其中，L为聚合物电解质的厚度，S为不锈钢垫片面积，R为测量得到的阻抗值。
电化学窗口：采用不锈钢和锂片夹住聚合物电解质，组装2032的扣式电池，进行线性伏安扫描(LSV)测量，起始电压2.8V，最高电位5.5V，扫描速度为1mV/S。
实施例7
将240mg的富锂锰基层状氧化物正极和45mg的导电剂乙炔黑均匀研磨40min；加入15mg粘结剂聚偏氟乙烯、15mg电解质混合液(实施例5)和150μL 1-甲基-2吡咯烷酮均匀研磨40min；涂敷在铝箔表面，在真空条件下80℃烘干8h；将极片裁成R＝12mm的圆片，采用上述实施例5有机无机复合电解质为电解质，金属锂作为负极组装固态锂离子电池。
实施例8
将240mg的钴酸锂氧化物正极和45mg的导电剂乙炔黑均匀研磨40min；加入15mg粘结剂聚偏氟乙烯、15mg电解质混合液(实施例5)和150μL 1-甲基-2吡咯烷酮均匀研磨40min；涂敷在铝箔表面，在真空条件下80℃烘干8h；将极片裁成R＝12mm的圆片，采用上述实施例5有机无机复合电解质为电解质，金属锂作为负极组装固态锂离子电池。
表一

Claims (10)

  1. 一种高离子电导率聚合物基复合固态电解质，其特征在于，原料包括如下组分：碳酸酯基聚合物、无机离子导体、引发剂或催化剂、锂盐和硅烷偶联剂；
    碳酸酯基聚合物占混合物的质量分数为10-96％，功能化硅烷偶联剂占混合物的质量分数为1-50％、导电锂盐占混合物的质量分数为1-50％，无机离子导体占混合物的质量分数为1-50％，引发剂或催化剂质量分数占混合物的质量分数为1-10％。
    所述碳酸酯基聚合物选自聚碳酸酯、聚碳酸乙烯酯，聚碳酸乙烯亚乙酯，聚烯丙基甲基碳酸酯，聚碳酸亚乙烯酯，聚氟代碳酸乙烯酯等聚合物中的一种或几种；碳酸酯基中C＝O双键可与硅烷偶联剂上的活泼H形成化学相互作用；
    所述无机锂离子导体材料为无机固态锂离子电解质，且该材料含有羟基、羧基或硫基中一种或至少两种的组合；
    所述硅烷偶联剂具有如式I所示结构：
    其中R1选自甲基，乙基，丙基其中的任意一种；R2选自胺丙基，胺乙基，巯基或脲基中的任意一种。
  2. 按照权利要求1所述的一种高离子电导率聚合物基复合固态电解质，其特征在于，所选导电锂盐为以下中的一种或几种：六氟磷酸锂(LiPF6)、高氯酸锂(LiClO4)、双三氟甲烷磺酰亚胺锂(LiTFSI)、双(三氟甲烷磺酰)甲基锂[LiC(SO2CF3)3]；
    所述引发剂或催化剂为以下中的一种：偶氮二异丁腈(AIBN)、偶氮二异庚腈(ABVN)、双(乙酰丙酮酸)二丁基锡、二月桂酸酯二丁基锡、偶氮二异丁酸二甲酯(AIBME)、过氧化苯甲酰(BPO)、铂金水(Pt)。
  3. 权利要求1所述的一种高离子电导率有机无机复合固态电解质的制备方法，其特征在于，包括以下步骤：
    (1)取无机离子导体材料、功能化硅烷偶联剂、有机溶剂原料搅拌混合均匀，在30-80℃下加热水解12-24小时，试剂及空气中的微量水即可，然后在80-120℃真空干燥箱去除溶剂，制备硅烷化的无机离子导体材料；
    (2)将步骤(1)得到的硅烷化无机离子导体材料、碳酸酯基聚合物、导电 锂盐、有机溶剂均匀搅拌；加入引发剂或催化剂搅拌均匀，形成电解质混合液；将上述电解质混合液涂覆到或浸入含有多孔支撑材料的聚四氟乙烯模具中，在60-120℃下加热固化4-12小时成膜。
  4. 按照权利要求3所述的方法，其特征在于，上述步骤(1)(2)中所选有机溶剂为以下中的一种或几种：N-甲基吡咯烷酮(NMP)、碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯脂、碳酸二甲酯、碳酸乙二酯、碳酸甲乙酯、γ-丁内酯、四氢呋喃、2-甲基四氢呋喃、乙腈、1,2-二甲氧乙烷、四乙二醇二甲醚、三乙二醇二甲醚、二乙二醇二甲醚、二甲亚砜。
  5. 按照权利要求3所述的方法，其特征在于，所述多孔支撑材料为纤维素无纺布、聚乙烯无纺布、聚丙烯无纺布、玻璃纤维无纺布、聚四氟乙烯无纺布中的一种或几种；优选的支撑材料可以改善聚合物基复合电解质的机械性能。
  6. 按照权利要求3所述的方法，其特征在于，偶联剂作为无机物和有机物之间的桥梁用于提供额外的离子传输通道，降低有机无机之间的界面电阻；利用分子间的相互作用及稳定的化学键提升聚合物基复合电解质的电化学稳定性，分子间的相互作用包括正空位作用，偶极-偶极相互作用，以及氢键相互作用等。
  7. 权利要求1或2所述的高离子电导率聚合物基复合固态电解质在锂离子电池中的应用。
  8. 一种包含上述高离子电导率聚合物基复合固态电解质的固态锂离子电池，其特征在于：包括正极、负极和置于正极和负极之间兼具隔膜和电解液功能的上述复合固态电解质，所述的复合固态电解质为权利要求1或2所述的高离子电导率聚合物基复合固态电解质。
  9. 按照权利要求8所述的锂离子电池，其特征在于：锂离子电池正极活性材料为钴酸锂(LiCoO2)、镍酸锂(LiNiO2)、锂离子氟磷酸锂、锂锰氧化物、锰酸锂、镍锰酸锂、富锂材料(LLOs)、磷酸锰铁锂、镍钴铝酸锂(NCA)、镍钴锰酸锂、磷酸铁锂(LiFeO4)、磷酸钒锂(Li3V2(PO4)3)中的一种或几种；负极活性材料为金属锂、金属锂合金、石墨、硬碳、锂金属氮化物、氧化锑、碳锗复合材料、碳硅复合材料、钛酸锂、锂钛氧化物中一种或几种；
    锂离子电池正极制备包括以下步骤：将占质量分数为50-90％的正极活性材料，占质量分数为5-30％的导电剂乙炔黑研磨混合；加入占质量分数为1-15％的 聚偏氟乙烯(PVDF)、1-15％电解质混合液和1-甲基-2吡咯烷酮(NMP)研磨混合，1-甲基-2吡咯烷酮(NMP)用于调节粘度；涂敷在铝箔表面，烘干；金属锂、金属锂合金可以直接作为相应的负极，其他负极制备包括以下步骤：将质量分数为45-80％的负极活性材料，质量分数为5-30％的导电剂乙炔黑研磨混合；加入质量分数为5-25％聚偏氟乙烯(PVDF)、1-甲基-2吡咯烷酮(NMP)研磨混合，1-甲基-2吡咯烷酮(NMP)用于调节粘度；涂敷在铜箔表面，烘干；
    上述电解质混合液优选为权利要求3中高离子电导率有机无机复合固态电解质制备过程中形成的电解质混合液。
  10. 按照权利要求8所述的锂离子电池，其特征在于：锂离子电池组装包括扣式电池和软包电池。
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